Two stage process for making ferromagnetic modified chromium dioxide



United States Patent Ofitice 3,371,043 Patented Feb. 27, 1968 3,371,043 TWO STAGE PROCESS FOR MAKING FERROMAG- NETIC MODIFIED CHROMIUM DIOXIDE Franz Hund, Krefeld-Bockum, and Wilhelm Abeck,

Cologne-Stamrnheim, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany N Drawing. Continuation of application Ser. No. 383,206, July 16, 1964. This application June 27, 1966, Ser. No. 560,892 Claims priority, application Germany, July 24, 1963,

F 40,333 11 Claims. (Cl. 252-6251) ABSTRACT OF THE DISCLOSURE Process of forming ferromagnetic chromium dioxide by a two-step doping process wherein chromium trioxide is heated with a guest component, or a precursor of such guest component, and the resulting product admixed with further guest component and this mixture heated.

This application is a continuation of application Ser. No. 383,206 filed July 16, 1964, now abandoned.

This invention relates to ferromagnetic chromium dioxide. It more particularly relates to a novel method for the preparation of ferromagnetic chromium dioxide and to a method of preparing ferromagnetic chromium dioxide containing modification elements in the crystal lattice thereof. 7

Ferromagnetic materials are used in many applications. They areemployed for instance in magnetic second recording tapes, drums and records, memory devices, cores, etc.

The formation of magnetic chromium oxides by heating CrO in a stream of oxygen has already been observed by I. Shukolf, J. Russ. Ges., 41 (1909), pp. 302-304.

According to R. S. Schwartz and co-Workers, Am Chem. Soc., 74, 1676 (1952), CrO can be prepared from CrO with traces of impurities of other oxides of chromium by heating for three hours at temperatures of 545 C. under an increased pressure of oxygen pressure.

Glemser and co-workers, Z.f.anorg. Chem., 277 (1954), p. 114 et seq. investigated the thermal degradation products of CrO radiographically and found that ferromagnetic CrO is present in the rutile lattice.

B. I. Thamer and co-workers, J. A. Chem. Soc, 79, 1957, pp. 547-550, prepared CrO contaminated by CrOOH by heating CrO with H O under pressure at temperatures of 300 to 325 C.

Ferromagnetic Cr0 in which other metal oxides are incorporated in the lattice is described, for example, in

US. patent specification 3,034,988. The magnetic properties of these CrO mixed phases are improved compared with the magnetic properties of pure chromium dioxide. Above all, mixed phases could be prepared with very different Curie temperatures.

In the preparation of these modified ferromagnetic chromium dioxides, finely divided CrO mixed with other metal oxides is usually heated in the presence of water to temperatures up to 500 C. under pressures of about 1 to 3000 atmospheres.

It is an object of the present invention to provide modified ferromagnetic chromium dioxide and a process for its preparation.

A further object is to provide novel chromium dioxide materials containing oxides or fluorides of other elements as guest components in the CrO host lattice.

Another object is to provide magnetic recording members having a magnetic track comprising the chemically modified ferromagnetic chromium dioxide.

Still other objects shall become apparent as the description proceeds.

For a number of purposes, e.g., for magnetic recording members, etc., the particle size and shape of the CrO crystals have an important influence on the optimum properties. It is therefore an important feature of all processes for the preparation of ferromagnetic materials to obtain a high yield of particles of a certain shape and size which have at the same time good magnetic properties.

In accord with and fulfilling the above-recited objects, this invention resides in one of its aspects in the provision of a process, whereby needle-shaped or prismatic particles of chromium dioxide mixed phases of a desired length and width or with an optimum ratio of length to width having excellent magnetic properties are produced. This process comprises heating, in a first part of the process, chromium trioxide with water in the presence of one or more guest components which are metal oxides or metal fluorides to temperatures of about to 500 0, preferably 100 to 300 C. and pressures of about 1 to 500 atmospheres, preferably about 50 to 300 atmospheres, and in one or several subsequent stages of the process, mixing with chromium trioxide and potential guest components the nuclei of chromium dioxide mixed phases derived from the first heating mediately referred to above, and subjecting such mixture to further hydrothermal treatment at temperatures of about 100 to 500 C. and at the pressures described above.

As guest components oxides or fluorides of such elements can be incorporated into the CrO lattice, the ions of which have radii between about 0.98 and 0.46 A., e.g., oxides or fluorides of Li, Na, K, Be, Mg, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi, Se, Te, Cu, Zn, Sc, Ti, Zr, Hf, V, Nb, Ta, Mo, W, U, M11, Tc, Re, Fe, Co, Ni. Ru, Pt and 1, preferably Sb, Se, Te, Co, Mn, Pt, Ru.

The above-mentioned elements can be applied in the form of their oxides or compounds which form the corresponding oxides under the reaction conditions, e.g., carbonates, chlorides, nitrates. In some cases, it might be preferred to apply the guest components in the form of their chemical elements, e.g., Te, Se, As, Sb, etc. The fluorides are preferably the difluorides having the lattice of rutile, e.g., MnF CoF NiF FeF ZnF etc.

In particular, it is also possible to incorporate mixtures of these oxides or fluorides into the Cr0 lattice whilst maintaining the rutile lattice or the polyrutile lattice, as described, for example, in US. patent specification 3,022,- 186. According to the US. patent mentioned hereinbefore, the preferred ratio of the sum of the added cations to the sum of the added anions is about 1:2.

Where mixtures of the above-referred oxides and/or fluorides are to be employed, salts, complex halogenides or -oxides as well as mixed phases of these elements can be applied. If the incorporation of Sb is intended to be used in combination with other elements, the following compounds can be employed: NaSbF Na SbCl Sb Te SnSb, CrSbO etc. The guest components are used in quantities up to 50 percent by weight referred to CrO in the first step of the process to obtain an endproduct with a content of guest component of 0.1 to 15 percent by weight referred to CrO The ratio by weight of the CrO and the guest components in the individual reaction steps is not specially critical and can be selected in accordance with the desired composition of the final product, however, it is not favorable to perform the first reaction step without the addition of guest components, and in the preferred embodiment of the process the whole amount of guest comtrioxide is mixed with an oxide or fluoride of one or more guest components with the addition of small quantities of water. This mixture is heated to temperatures of 100 to 500 C. for about /2 to 4 hours in a reaction vessel of inert material in an autoclave containing water and under an excess pressure of an inert gas and/ or oxygen or without the use of a foreign gas, and then kept for about 1 to hours under constant conditions of temperature and pressure. After cooling,the reaction product is powdered and washed free from chromate with water, filtered and dried under mild conditions. The nuclei of the chromium dioxide mixed phases are then again mixed with chromium trioxide and water to which guest components may again be added and then placed in an autoclave containing water, as indicated above, under excess pressure of inert gas and/or oxygen or without foreign gas, and heated to temperatures of 100 to 500 C. and again left for about 1 to 10 hours. at constant pressure and temperature.

The modified chromium dioxide prepared by the new process is needle-shaped with a ratio of length to width of about 10:1.

It has very good magnetic properties, e.g., the chromium dioxide which contains antimony oxide has a saturation magnetization Bmax/tr of about 1000 gauss. g.- .cm. Further, values of about 450 gauss. gfhcm. were determined for the saturation remanence BR/O' and the coercive force iHc was found to be about 280 to 400 oersted.

A magnetic recording member with very good properties can be prepared as follows: 2.16 kg. of needle-shaped chromium dioxide containing antimony throughout the lattice are ground in a ball mill for 14 hours in a solution of 108 grams of a vinyl chloride homopolymer.

The chromium dioxide lacquer suspension thus prepared is cast on to a p thick polyester foil. The resulting layer is passed through a homogenous magnetic field of about 1000 oersted while still wet on the surface.

A layer containing 11.5 g./m. CrO has a thickness of 6p. The layer has a B /B value of 0.88. The surface resistance is 1.10 ohm per cm.

The definitions of the magnetic values given above as Well as the methods for their determination are given in R.Ch.H. Miiller Mitteilungen aus den Forschungslabor. der AGFA, Leverkusen-Miinchen, Verlag Springer 1955, pp. 320-325.

The electroacoustic measurements have been made according to DIN 455l2 p. 2 and according to DIN Example 1 (a) Formation of nuclei.--119.0 g. CrO and 8.00 g. Sb O +2.00 ml. H O are well mixed, filled into a Pyrex glass tube 40 mm., 1:150 mm.), and placed above water in an autoclave under an oxygen pressure of 100 atmospheres. Afterwards the system is heated at 300 C. for about 80 minutes whereby the pressure is adjusted to 200 atmospheres and these conditions are maintained for 8 hours.

After cooling, the substance is powdered, washed free from CrO with distilled water, filtered and dried in a vacuum at 40 C. Yield: 97 g.; magnetic data: Br/a=2l1 G.g.- .cm. iHc=197 oe.

(b) Pigment formation-119.0 g. CrO +8.00 g. CrO nuclei from (1a)+16.0 ml. H O are well mixed, filled into a Pyrex glass tube (see above), put under an oxygen pressure of 100 atmospheres above water in an autoclave and then heated at 300 C. for 80 minutes (pressure approximately 270 atmospheres) and maintained under these conditions for 8 hours.

Further working up as with the nuclear material.

Yield: g.; magnetic data: Br/tr 450 G.g. .cm.

iHc=257 oe.

(c) As comparative showing experiment (la)-nuclei formation-was repeated under the same conditions but performed in one case for 16 hours and in another case after 32 hours. Both end productsare worked'up'as under (la) and their magnetic properties investigated;'

(10) 16 hours Br/a 219 G.g. .cm. iHc=230 oe.

(1c) 32 hours Br/a 192 G.g.- .crn. iHc=170 oe.

Example 2 (a) Formation of nuclei.1l9.0 g. CrO +8.00 g. Sb O +2.0 ml. H O are well mixed, filled into a Pyrex glass tube, placed above water in an autoclave under an oxygen pressure of 100 atmospheres and then heated for about 80 minutes at 280 C. and the pressure is then adjusted to 200 atmospheres and these conditions maintained for 8 hours. After cooling, the substance is powdered, washed free from CrO with distilled H 0 and dried in a vacuum at 40 C.

Yield: 94 g.; magnetic data: Br/ r=l89 G.g. .cm.. iH-c=204 oe.

(b) Pigment f0rmation.ll9.0 g. CrO +8.0 g. nuclei (2a)+20.0 ml. H O are well mixed, filled into a Pyrex glass tube, placed above water inan autoclave under an oxygen pressure of 120 atmospheres and then heated for about 80 minutes at 300 C. and kept at this temperature for 8 hours (final pressure about 270 atmospheres). The preparation is powdered after cooling, washed free from CrO with distilled'H O, filtered and dried in a vacuum at 40 C.

Yield: g.; magnetic data: Br/a-=448 G.g.- .cm. iHc=342 oe.

After drying in air at 105 C., the magnetic data are: Br/a:440 G.g.- .cm. iHc=342 oe.

Example 3 (a) Formation of nuclei.ll9.0 g. CrO +8.00 g. Sb O are well mixed, poured into a Pyrex glass tube and placed above water in an autoclave under an oxygen pressure of 100 atmospheres and then heated at 260 C. for about 80 minutes and the pressure is then adjusted to 200 atmospheres and these conditions maintained for 8 hours.

After cooling, the substance is powdered, washed free from CrO with distilled H O, filtered and dried in a vacuum at 40 C. w

Yield: 93 g.; magnetic data: Br/o'=247 .G.g.- .cm. iHc=237 oe.

(b) Pigment formation-419.0 g. CrO +8.00 g. nuclei (3a)+8.0 ml. H O are well mixed, filled into a Pyrex glass tube, placed above water in an autoclave under an oxygen pressure of atmospheres and then heated at 300 C. for about 80 minutes and kept at this temperature for 8 hours (final pressure about 270 atmospheres). After cooling, the preparation is powdered, washed free from CrO with distilled water, filtered and dried in-a vacuum at 40 C.

Yield: 99 g.; magnetic data: Br/a=455 G.g. .cm.

iHc=266 oe.

Example 4 (a) Formation of nuclei as in Example 2a; a V4A (stainless steel) tube is used instead of a Pyrex glass tube.

Yield: 93 g.; magnetic data: Br/tr=242 G.g. .cm. iHc=252 oe. v

(b) Pigment formation-119.0 g. CrO +8.00 g. nuclei (4a)+16.00 ml. H O are well mixed, poured into a V4A tube, heated at 300 C. for about 80 minutes in an autoclave without foreign gas and kept at this temperature for 8 hours (final pressure about 90 atmos- (a) Formation of nuclei as in Example 1.

Yield: 94 g.; magnetic data: Br/o=221 G.g. .cm. iI-Ic=204 e. 7

(b) Pigment formation-119.0 g. CrO +8.00 g. nuclei (a)+l6.0 ml. H O are well mixed, filled into a V4A tube, put under a pressure of 60 atmospheres O +60 atmospheres N over H O in an autoclave, and then heated at 300 C. for about 80 minutes (pressure about 270 atmospheres) and kept thus for 8 hours. Further working up as with the other examples.

Yield: 102 g.; magnetic data: Br/a=470 G.g." .cm. iHc=349 oe.

Example 6 (a) Formation of nuclei as in (5a).

(b) Pigment formation as in (5a) except that a pressure of 120 atmospheres N was used instead of 60 atmospheres 0 -1-60 atmospheres N Yield: 104 g.; magnetic data: Br/cr=456 G.g. .cm. iHc=325 oe.

Example 7 (a) Formation of nuclei.1l9.0 g. CrO +8.00 g. Sb O +2.0 ml. H O are well mixed, filled into a V4A tube, placed in an autoclave under a pressure of over 50 atmospheres O and 50 atmospheres N and then heated at 280 C. for 80 minutes and the pressure is then adjusted to 200 atmospheres and these conditions maintained for 8 hours. Working up as in the other examples.

Yield: 95 g.; magnetic data: Br/a=l85 G.g. .cm. iHc=168 oe.

(b) Pigment formation.-1 19.0 g. CrO +8.00 g. nuclei (7a)+16.0 ml. H O are well mixed, filled into a V4A tube, heated at 300 C. for about 80 minutes in an autoclave above H O Without the addition of foreign gases and maintained at this temperature for 8 hours (final pressure 90 atmospheres). Working up as in the other examples.

Yield: 102 g.; magnetic data: Br/a=417 G.g.- .cm. iHc=387 oe.

Example 8 (a) Formation of nuclei as in Example 2a.

Yield: 93 g.; magnetic data: Br/r=242 G.g.- .cm. iHc=252 0e.

(b) Pigment formation as in Example 2b.

The material was kept for only 1 hour instead of for 8 hours at 300 C. at a final pressure of 270 atmospheres.

Yield: 92 g.; magnetic data: Br/a=451 G.g. .cm. iHc=338 oe.

Example 9 (a) Formation of nuclei.119.0 g. CrO 4.00 g. TeO|-2.00 ml. H O are mixed well, introduced into a V4A tube and put under an oxygen pressure of 100 atmos pheres in an autoclave above H 0 and then heated to 280 C. in about 80 minutes, the pressure being then adjusted to 200 atmospheres and these conditions maintained for 8 hours. After cooling, the substance is powdered, washed free from CrO with distilled H O, filtered and dried in a vacuum at 400 C.

Yield: 99.3 g.; magnetic data: Br/a=296 G.g. .cm. iHc=267 0e.

(b) Pigment formation-419.0 g. CI'O3+8-00 g. Cr0 nuclei from 9a+16.0 ml. H O are mixed well, filled into a V4A tube, put under an oxygen pressure of 120-atmospheres in an autoclave of above H 0 and then heated for 80 minutes at 300 C. (pressure 270 ats.) and maintained thus for 8 hours. Further working up as for the nuclear material.

6 Yield; 101.7 g.;.magnetic data: Br/a=445 G.g. .cm.

' iHc=286 oe.

Example 10 (a) Formation of nuclei.-ll9.0 g. CrO +8.0O g. TeO +2.00 ml. H O are mixed well and the further treat ment is'as in Example 9. 1

Yield: 104.5 g.; magnetic data: Br/a=300 G.g.- .cm. iHC=270 oe.

(b) Pigment formation-119.0 g. CrO +8.00 CrOg nuclei from l0a+16.0 ml. H O are mixed well and then worked up as in Example 9b.

Yield: 100.6 g.; magnetic data: Br/a=443 G.g." .cm. iHc=282 oe.

Example 11 (a) Formation of nuclei.59.5 g. CrO +2.00 g. PtO+1.0 ml. H O are mixed well, introduced into a V4A tube and put under an oxygen pressure of atmospheres in an autoclave above H 0 and then heated to 280 C. in about 60 minutes and the pressure is then adjusted to 200 atmospheres and these conditions maintained for 8 hours. After cooling, the substance is powdered, washed free from CrO with distilled water, filtered and dried in a vacuum at 40 C.

Yield: 50.6 g.; magnetic data: Br/e=246 G.g. .cm. iHc=8l oe.

(b) Pigment formation.-119.0 g. CrC +8.00 g. CrO nuclei from 11a+16.0 ml. H O are mixed. well, filled into a V4A tube, put under an oxygen presure of 120 atmospheres in an autoclave above water and then heated to 300 C. for about 60 minutes (pressure 270 atmospheres) and kept under these conditions for 8 hours. Further Working up as for the nucleus.

Yield: 103.4 g.; magnetic data: BI/0'=309 G.g. .cm. iHc= oe.

Example 12 (a) Formation of nuclei.-59.5 g. CrO +4.00 g. RuO +1.0 ml. H O are mixed Well and then treated as in Example 11a.

Yield: 43.0 g.; magnetic data: Br/ r=182 G.g.- .cm. iHc=118 oe.

(b) Pigment formation.-1l9.0 g. CrO +8.00 g. CrO nuclei from 12a+16.0 ml. H O are mixed well and then worked. up as in Example 11b.

Yield: 104.0 g.; magnetic data: Br/a=279 G.g. .cm. iHc=91 0e.

' Example 13 (a) Formation of nuclei.--ll9.0 g. CrO +1.947 g. MnO+8.00 g. Sb O +2.0 ml. H O are mixed well, introduced into a V4A tube and put under an oxygen pressure of 100 atmospheres in an autoclave above H 0 and then heated to 280 C. for about 60 minutes and the pressure is then adjusted to 200 atmospheres and these conditions maintained for 8 hours. ,After cooling, the substance is powdered, washed free from CrO with distilled water, filtered and dried in a vacuum at 40 C.

Yield: 102.8 g.; magnetic data: Br/a=222 G.g.- .cm'. iHc=236 0e.

(b) Pigment f0rmation.e1l9.0 g. CrO +8.00 g. CrO nuclei from 13a+16.0 ml. H O are mixed well, filled into a V4A tube and put under an oxygen pressure of 120 atmospheres in an autoclave above H 0 and heated to 300 C. for about 60 minutes (pressure 270 atmospheres) and kept under these conditionsfor 8 hours. Further working up as for the nuclei.

Yield: 104.3 g.; magnetic data: Br/t7=.498 G.g..- .cm. iHc=388 0e.

Example 14 (a) Formation of nuclei.1 19.0 g. CrO +4.98 Se+2.0 ml. H O are mixed well, introduced into a V4A tube and put under an oxygen pressure of 100 atmospheres in an autoclave above H 0 and then heated to 280 C. in about 60 minutes and the pressure is then adjusted. to 2-00 atmospheres and these conditions maintained for 8 hours. After cooling, the substance is powdered, washed free from CrO with distilled water, filtered and dried in a vacuum at 40 C.

Yield: 68.0 g.; magnetic data: Br/a:32 G.g. .cm.

iHc=ST oe. I 1

(b) Pigment formation.l 19.0 g. CrO +8.00 g.CrO nuclei "from l4a+l6.0 ml; H O are mixed well, filled into a V4A tube, put under an oxygen pressure of 120 atmospheres in an autoclave above'H O and then heated to 300 C. in about 60 minutes (pressure 270 atmospheres) and maintained under these conditions for 8 hours. Fur.- ther working up as for the nuclear material.

Yield: 99.0 g.; magnetic data: Br/t1=276 G.g. .crn. iHc=81 oe.

Example 15 (a) Formation of nuclei.-ll9.0 g. Cro t-8.00 g. SeO +2.0 ml. H O are mixed well, introduced into a V4A tube and put under an oxygen pressure of 100 atmospheres in an autoclave above H and then heated to 250 C. for about 60 minutes and the pressure is then adjusted to 170 atmospheres and these conditions maintained for 8 hours. After cooling, the substance is powdered, washed free from CrOE- with distilled water, filtered and dried in a vacuum at 40 C.

Yield: 74.5 g.; magnetic data: Br/a=1l G.g. .cm. iHc=l oe.

(b) Pigment formation-119.0 g. CrO +8.0O g. CrO nuclei from a+l6.0 ml. H O are mixed Well, filled into a V4A tube, put under an oxygen pressure of 120 atmospheres in an autoclave above H 0 and then heated to 300 C. in about 60 minutes (pressure 270 atmospheres) and maintained under these conditions for 8 hours. Further working up as for the nuclear material.

Yield: 102.3 g.; magnetic data: Bi /0:225 G.g. .cm. iHc=67 oe.

Example 16 (a) Formation of nuclei.1l9.0 g. CrO +8.00' g. PbO+2.0 ml. H O are mixed well, introduced into a V4A tube and put under an oxygen pressure of 100 atmospheres in an autoclave above H 0 and then heated to 280 C. in about 60 minutes and the pressure is then adjusted to 200 atmospheres and these conditions powdered, washed free from CrO with distilled water, filtered and dried into a vacuum at 40 C.

Yield: 99.4 g.; magnetic data: Br/a:2l7 G.g. .cm. iI- Ic=.62 oe.

(b) Pigment formation.l19.0 g. CrO -i-8.00 g. CrO nuclei from l6a+16.0 ml. H O are mixed well, filled into a V4A tube, put under an oxygen pressure of 120 atmospheres in an autoclave above H 0 and then heated to 300 C. in about 60 minutes (pressure 270 atmospheres) and kept under these conditions for 8 hours. Further workingv up as for the nuclear material.

Yield: 103.3 g.; magnetic data: Br/a=28l G.g." .cm. iHc=75 oe.

Example 17 (a) Formation of nuclei.1l9.0 g. CrO 8.00 g. PbO +2.0 ml. H O are mixed well, introduced into a V4A tube and put under an oxygen pressure of 100 atmospheres in an autoclave above H 0 and then heated to 280 C. in about 60 minutes, and the pressure is then adjusted to 200 atmospheres and these conditions maintained for 8 hours. After cooling, the substance is powdered, washed free from CrO with distilled H O, filtered and dried in a vacuum at 400 C.

Yield: 103.9 g.; magnetic data: Br/a'=233 G.g.- .cm. iHc=69 oe.

(b) Pigment '70rmation.1l9.0 g. CrO +8.O0 g. CrO nuclei from 'l7a+-l 6.0 ml. H O are mixed well, filled into a V4A tube, put under an oxygen pressure of 120 atmospheres in an autoclave above H 0 and then heated to 300 C. in about 60 minutes (270 atmospheres pressure) and kept under these conditions for 8 hours, further working up as for the nucleus.

Yield: 102.6 g.; magnetic data: Br/a:27l G.g. .cm. iHc=83 oe.

Example 18 (a) Formation of nuclei.ll9. 0 g. CrO +8.00 g. U0 in the form of UO -2H O+2.0 mL H O'are mixed well, introduced into a V4A tube and put under an oxygen pressure of atmospheres in an autoclave above H 0 and then heatedto 280 C. in about 60 minutes, and the pressure is then adjusted to2=00 atmospheres and these conditions maintained for 8 hours. After cooling,the substance is powdered, washed free from CrO, with distilled water, filtered and dried in a vacuum at 40 C. 7

Yield: 84.3 g.; magnetic data: Br/a=l47 G.g. .cm. iHc=73 oe.

(b) Pigment formation-119.0 g. CrO +8.00 g. CrO nuclei from 18a+16.0 ml. H O are mixed well, filled into a V4A tube, put under an oxygen pressure of atmospheres in an autoclave above H 0 and then heated to 300 C. in about 60 minutes (pressure 270 atmospheres) and kept under these conditions for 8 hours. Further working up as for the nucleus.

Yield: 106.8 g.; magnetic data: Br/a=249 G.g. .cm. iHc=6l oe.

Example 19 (a) Formation of nnclei.ll9.0 g. CrO +5.82 g. Te (met.)+2.0 ml. H O are mixed well, introduced into a V4A tube and put under an oxygen pressure of 100 atmospheres in an autoclave above H 0 and then heated to 280 C. in about 60 minutes and the pressure is then adjusted to 200 atmospheres and these conditions maintained for 8 hours. After cooling, the substance is powdered, washed free from CrOE- with distilled water, filtered and dried in a vacuum at 40 C.

Yield: 104.8 g.; magnetic data: Br/ r:270 G.g. .cm. iHc= oe.

(b) Pigment formation.l19.0 g. CrO +8.00 g. CrO nuclei from 19a+16.0 ml. H O are mixed well, filled into a V4A tube, put under an oxygen pressure of 120 atmospheres in an autoclave over H 0 and then heated to 300 C. in about 60 minutes (pressure 270 atmospheres) and kept under these conditions for 8 hours. Further Working up as for the nuclear material.

Yield: 101.8 g.; magnetic data: Br/a=45l G.g.- .cm. iHc=274 oe.

Example 20 (a) Formation of nuclei.-ll9.0 g. CrO +8.00 g. TeO +2.O ml. H O are mixed well, introduced into a V4A tube and put under an ox gen pressure of 100 atmospheres in an autoclave over H 0 and then heated to 280 C. in about 60 minutes, the pressure is adjusted to 200 atmospheres and these conditions are maintained for 8 hours. After cooling, the substance is powdered, washed free from CrO with distilled water, filtered and dried in a vacuum at 40 C. 7

Yield: 105.6 g; magnetic data: Br/o'=247 G.g. .cm.

iHc=l43 oe.

(b) Pigment formati0n.l19.0 g. CrO +8.0O g. CrO nuclei from 20a+l6.0 ml. H O are mixed Well, intro: duced into a V4A tube, put under an oxygen pressure of 120 atmospheres in an autoclave above H 0 and then heated to 300 C. in about 60 minutes (pressure 270 atmospheres) and kept under these conditions for. 8 hours. Further working up as for the nuclear material.

Yield: 98.7 g.; magnetic data: Br/o=482 G.g. .cm.

iHc=393 oe.

Example 21 (a) Formation of nuclei-419.0 g. CrO +2.057 g. C00 in the form of carbonate+8.00 g. Sb +2.0 ml. H O are mixed well, introduced into a V4A tube, put under an oxygen pressure of 100 atmospheres in an autoclave about H 0 and then heated to 280 C. in about 60 minutes and the pressure is adjusted to 200 atmospheres and these conditions maintained for 8 hours. After cooling, the substance is powdered, washed free from CrO with distilled H O, filtered and dried in a vacuum at 40 C.

Yield: 99.6 g.; magnetic data: Br/a=213 G.g. .cm. iHc=220 e.

(b) Pigment formation-119.0 g. C1'O +8.00 g. C nuclei from 21a+16.0 ml. H O are mixed well, filled into a V4A tube, put under an oxygen pressure of 120 atmospheres in an autoclave over H 0 and then heated to 300 C. in about 60 minutes (pressure 270 atmospheres) and kept under these conditions for 8 hours. Further working up as for the nuclear material.

Yield: 102.9 g.; magnetic data: Br/a=477 G.g.- .cm. iHc=420 oe.

We claim:

1. Process for the production of a ferromagnetic material with a r utile type lattice containing at least 85% by weight of Cr0 as host component and modifying additives of the group consisting of oxides and fluorides as guest components in an elfective amount of up to by weight comprising the steps of (a) heating a mixture containing CrO and a chemical individual capable of yielding, under the conditions hereinafter set forth, the guest component selected from the group consisting of oxides and fluorides of cations having radii between 0.98 and 0.46 A in an aqueous medium under hydrothermal conditions at a temperature of between 100 and 500 C. and a pressure of between 1 and 500 atmospheres for 0.5 to 10 hours to form crystallization nuclei consisting of CrO and the guest component and washing the resultant product substantially free from CrO- with water;

(b) heating the crystallization nuclei produced in step (a) with a product of the group consisting of CrO and a mixture of CrO and the guest component in an aqueous medium under hydrothermal conditions at a temperature between 100 to 500 C. and a pressure between 1 to 500 atmospheres for 1 to 16 hours to etfect growth of the crystallization nuclei up to a final length of about 2 and (c) working up the final product by filtering,

and drying,

the ratio by weight of CrO and the guest component in the steps (a) and (-b) being adjusted to obtain product crystals consisting of at least 85% by weight of CrO and 0.1 to 15 by weight of said guest component.

2. Process according to claim 1 which comprises heating the reaction mixture of CrO and the guest component in step (a) at a temperature of between 100 and 300 C. and a pressure of between 50 and 300 atmospheres.

washing 3. Process according to claim 1 wherein said cation is a member of the group consisting of Li, Na, K, Be, Mg, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi, Se, Te, Cu, Zn, Sc, Ti, Zr, Hf, V, Nb, Ta, Mo, W, U, Mn, Tc, Re, Fe, Co, Ni, Ru, Pt and J.

4. Process according to claim 1 wherein the guest component is applied as chemical individual capable of yielding an oxide under the conditions of step (a).

5. Process according to claim 4 wherein the guest component is applied as a chemical individual selected from the group consisting of carbonates, halides, nitrates, sulfates and sulfides.

6. Process according to claim 1 wherein said cations are platinum.

7. Process according to claim 1 wherein said cations are antimony.

8. Process according to claim 1 wherein said cations are tellurium.

9. Process according to claim 1 wherein said cations are manganese.

10. Process according to claim 1 wherein said cations are cobalt.

11. Process according to claim 1 which comprises the steps of (a) heating a mixture containing CrO and the guest component in an amount up to 50% by weight referred to CrO in an aqueous medium under hydrothermal conditions at a temperature between 100 to 500 C. and a pressure between 50 to 300 atmospheres to form crystallization nuclei consisting of CrO and the guest component and (b) heating the crystallization nuclei produced in step (a) with an additional amount of CrO to yield final crystals consisting of at least by weight of CrO and 0.1 to 15% by weight of the guest component in an aqueous medium under hydrothermal conditions at a temperature of to 500 C. and a pressure of to 300 atmospheres to effect growth of the crystallization nuclei up to a final length of about 2n.

References Cited UNITED STATES PATENTS 2,923,683 2/1960 Ingraham 252-625 3,034,988 5/1962 Ingraham 252-625 3,068,176 12/1962 Ingraham 252-625 3,078,147 2/1963 Cox 252-625 3,243,260 3/1966 Kubota et al 252-625 3,278,263 10/1966 Cox 252-625 HELEN M. MCCARTH, Primary Examiner.

TOBIAS E. LEVOW, ROBERT D. EDMONDS,

Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,371 ,043 February 27 1968 Franz Hund et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 9, line 33,

CR0 should read CR0 Signed and sealed this 23rd day of September 1969.

(SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer Commissioner of Patents WILLIAM E. -SCHUYLER, IR. 

